CN101821894B - Method for producing lithium ion conductive solid electrolyte - Google Patents
Method for producing lithium ion conductive solid electrolyte Download PDFInfo
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- CN101821894B CN101821894B CN2008801105450A CN200880110545A CN101821894B CN 101821894 B CN101821894 B CN 101821894B CN 2008801105450 A CN2008801105450 A CN 2008801105450A CN 200880110545 A CN200880110545 A CN 200880110545A CN 101821894 B CN101821894 B CN 101821894B
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- solid electrolyte
- sulfide
- solvent
- ion conductive
- lithium
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 35
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 15
- KHDSWONFYIAAPE-UHFFFAOYSA-N silicon sulfide Chemical compound S=[Si]=S KHDSWONFYIAAPE-UHFFFAOYSA-N 0.000 claims abstract description 8
- VDNSGQQAZRMTCI-UHFFFAOYSA-N sulfanylidenegermanium Chemical compound [Ge]=S VDNSGQQAZRMTCI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 238000005987 sulfurization reaction Methods 0.000 claims description 7
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 abstract 1
- ZVTQDOIPKNCMAR-UHFFFAOYSA-N sulfanylidene(sulfanylideneboranylsulfanyl)borane Chemical compound S=BSB=S ZVTQDOIPKNCMAR-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000011521 glass Substances 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 208000002173 dizziness Diseases 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 150000003738 xylenes Chemical class 0.000 description 3
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- -1 carrene Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Abstract
The present invention provides a method for producing a lithium ion conductive solid electrolyte, comprising a step of bringing one or more compounds selected from the group consisting of phosphorus sulfide, germanium sulfide, silicon sulfide and boron sulfide into contact with lithium sulfide in a hydrocarbon solvent.
Description
Technical field
The present invention relates to a kind of method for producing lithium ion conductive solid electrolyte.More particularly, relate to a kind of special installation ground that can under lower temperature, not use and in industry, advantageously make the method for lithium-ion-conducting solid electrolyte.
Background technology
In recent years, be used as personal digital assistant device, mobile electron machine, household small-size electrical storage device, increase with the demand of motor as the lithium battery of the main power utilization of the two-wheeled motorcycle of electric power source, mixed power electric car etc.
Because used solid electrolyte contains flammable organic substance mostly in the lithium battery now, might cause catching fire when therefore generation is unusual in battery etc., the fail safe of battery is guaranteed in expectation.In addition; For the reliability that improves impact or vibration, further improve energy density and from the strong social demand as far as earth environment cleaning and high efficiency energy conversion system, the fully solid lithium secondary battery of the solid electrolyte that use constitutes with non-flame properties solid material is developed in urgent expectation.
As non-flame properties solid electrolyte, studying sulfide-based solid electrolyte.With regard to its manufacturing, have with raw material under the vacuum or under inert atmosphere with the method for high-temperature process, at room temperature use the planet-shaped ball mill to carry out the method for mechanical lapping.But, be that which kind of method all needs special devices, be not suitable for producing in enormous quantities.
The inventor etc. are to above-mentioned problem; Proposed following method, that is, in organic solvent, reacted through making raw material; Can under lower temperature, not need special installation ground in industry, advantageously to make lithium-ion-conducting solid electrolyte (with reference to patent documentation 1).Specifically, use N-N-methyl-2-2-pyrrolidone N-etc., lithium sulfide and phosphoric sulfide are reacted with the homogeneous solution form as non-proton organic solvent.
But even non-proton organic solvent, the higher solvent of N-N-methyl-2-2-pyrrolidone N-isopolarity dissolves phosphoric sulfide easily; Become and improve reactive factor; Yet on the other hand, since strong with the solvation of lithium sulfide, therefore also there is easy problem remaining in the lithium sulfide product.
In the technology of patent documentation 1, though also can embody the ionic conductance of regulation through in fact fully removing residual N-N-methyl-2-2-pyrrolidone N-, remain sufficient inadequately level.But,, therefore have the elongated problem of manufacturing process owing to need repeated multiple times to utilize the solvent distillation under the solid electrolyte that cleaning generated of non-polar solven, the decompression to remove.
In addition; Because of removing N-N-methyl-2-2-pyrrolidone N-isopolarity solvent is remained under the situation in the product by the solvent distillation of commonsense method; Can cause the reduction of extreme ionic conductance, need improve from realizing the viewpoint that stabilized products is supplied with.And, if the temperature at high temperature when the distillation of polar solvent is removed is too high, then might be owing to make the ionic conductivity reduction of solid electrolyte with the reaction of solvent.
Residual polar solvent also can cause the reduction of battery performance, the corrosion of cell (Cell) sometimes, needs as far as possible fully to remove.In addition, the solvent price height that N-N-methyl-2-2-pyrrolidone N-etc. are special considers that from the cost aspect also expectation has suitable solvent.
In the patent documentation 2, put down in writing the manufacturing approach of the raw materials mix powder being utilized the solid electrolyte that special machines such as grindstone handle under lower temperature.But owing to need special machine, and raw meal is attached on the wall of device, and it is poor therefore to make efficient.
Patent documentation 1: No. the 2004/093099th, International Publication
Patent documentation 2: japanese kokai publication hei 11-144523 communique
Summary of the invention
The objective of the invention is to, provide and not use special installation ground easily to make the method for lithium-ion-conducting solid electrolyte.
In the manufacturing of the solid electrolyte that has used organic solvent,, preferably use the high solvent of polarity in order to improve the reactive dissolubility that preferably improves raw material for this reason.On the other hand, owing to the high solvent of polarity residues in the final products easily, so the performance of the solid electrolyte of gained might reduce.Under opposite like this condition, discoveries such as the inventor through using the hydrocarbon system solvent as solvent, just can be kept reactivity, the solvent in the minimizing final products residual, thus accomplished the present invention.
According to the present invention, following method for producing lithium ion conductive solid electrolyte can be provided.
1. method for producing lithium ion conductive solid electrolyte comprises making being selected from the operation that more than one compound and the lithium sulfide in phosphoric sulfide, germanium sulfide, silicon sulfide and the sulfuration boron contacts in the hydrocarbon system solvent.
2. according to the method for producing lithium ion conductive solid electrolyte described in 1, wherein, the contact temperature in the hydrocarbon system solvent is more than 80 ℃ below 300 ℃.
3. according to the method for producing lithium ion conductive solid electrolyte described in 1 or 2, wherein, with the further heat treated under 200 ℃～400 ℃ temperature of the solid electrolyte that utilizes above-mentioned contact operation to obtain.
4. according to any described method for producing lithium ion conductive solid electrolyte in 1～3, wherein, the average grain diameter of above-mentioned lithium sulfide is below the 10 μ m.
According to the present invention, can not use special machine or special solvent, short time and easily make lithium-ion-conducting solid electrolyte.
Embodiment
Method for producing lithium ion conductive solid electrolyte of the present invention comprises making be selected from the operation that more than one compound and the lithium sulfide in phosphoric sulfide, germanium sulfide, silicon sulfide and the sulfuration boron contacts in the hydrocarbon system solvent.
For the phosphoric sulfide that uses among the present invention, germanium sulfide, silicon sulfide and sulfuration boron, not special the qualification can be used commercially available material.In the middle of them, preferred phosphoric sulfide.In the middle of phosphoric sulfide, more preferably phosphorus pentasulfide.
The lithium sulfide that uses among the present invention for example can synthesize with the method for record in No. the 3528866th, the Japan Patent.Especially preferably utilize the method etc. of record in No. the 2005/040039th, the International Publication synthetic, purity is the material more than 99%.
Lithium sulfide preferably utilizes pulverizing to wait processing in advance, and making average grain diameter is below the 10 μ m.Be preferably especially below the 5 μ m.If average grain diameter is little, then can shorten the reaction time, in addition, the conductivity of the solid electrolyte of gained improves easily.
Hydrocarbon system solvent as as solvent can use saturated hydrocarbons, unsaturated hydrocarbons or aromatic hydrocarbon.
As saturated hydrocarbons, can enumerate hexane, pentane, 2-ethyl hexane, heptane, decane, cyclohexane etc.
As unsaturated hydrocarbons, can enumerate hexene, heptene, cyclohexene etc.
As aromatic hydrocarbon, can enumerate toluene, xylenes, decahydronaphthalenes, 1,2,3,4-naphthane etc.
In the middle of them, preferred especially toluene, xylenes.
The hydrocarbon system solvent is preferably dehydrated in advance.Specifically, be preferably below 100 ppm by weight, be preferably especially below 30 ppm by weight as moisture.
In addition, also can in the hydrocarbon system solvent, add other solvent as required.Specifically, can enumerate ketones such as acetone, MEK; Ethers such as oxolane; Alcohols such as ethanol, butanols; Ester classes such as ethyl acetate etc.; Halogenated hydrocarbon such as carrene, chlorobenzene etc.
Among the present invention, more than one the compound (following brief note sometimes is compd A) that is selected from phosphoric sulfide, germanium sulfide, silicon sulfide and the sulfuration boron is contacted in the hydrocarbon system solvent with lithium sulfide.
The addition of lithium sulfide preferably with respect to the 30～95mol% that adds up to of lithium sulfide and compd A, more preferably is made as 40～90mol%, especially preferably is made as 50～85mol%.
The amount of hydrocarbon system solvent is preferably following degree,, becomes solution or pulpous state as the lithium sulfide of raw material and compd A because of the interpolation of solvent that is.As a rule, the addition with respect to the raw material (total amount) of 1 liter of solvent reaches about 0.001～1Kg.Be preferably 0.005～0.5Kg, be preferably 0.01～0.3Kg especially.
Lithium sulfide is contacted in the hydrocarbon system solvent with compd A.The temperature of this moment is 80～300 ℃ as a rule, is preferably 100～250 ℃, more preferably 100～200 ℃.In addition, as a rule, the time is 5 minutes～50 hours, is preferably 10 minutes～40 hours.
And temperature or time also can make up based on some conditions.
In addition, preferably stir during contact.Preferably under inert gas atmospheres such as nitrogen, argon gas, carry out.The dew point of inert gas is preferably below-20 ℃, is preferably especially below-40 ℃.Pressure is normal pressure～100MPa as a rule, is preferably normal pressure～20MPa.
After contact is handled, the solid portion that generates and separated from solvent are reclaimed solid electrolyte.Separation can be implemented with decant, filtration, drying or their known method such as combination.
Among the present invention, preferably will utilize solid electrolyte that above-mentioned contact operation obtains further under 200 ℃～400 ℃ conditions, more preferably under 230～350 ℃ of conditions, carry out heat treated.Like this, the ionic conductivity of solid electrolyte will improve.
The time of heat treated is preferably 0.1～24 hour, is preferably 0.5～12 hour especially.
And heat treated is preferably carried out under inert gas atmospheres such as nitrogen, argon gas.The dew point of inert gas is preferably below-20 ℃, is preferably especially below-40 ℃.Pressure as a rule is decompression～20MPa, and preferred drying under reduced pressure perhaps makes the inert gas circulation under normal pressure.
In the manufacturing approach of the present invention,, therefore can make solid electrolyte in the hydrocarbon system solvent with common apparatus such as common reactive tank or autoclaves because raw material is contacted.That is, do not need can withstand high temperatures special devices such as equipment or ball mill.
In addition, through using the hydrocarbon system solvent, can reduce the quantity of solvent that residues in the solid electrolyte.Thus, even the processing of removing of residual solvent such as do not clean, also can make ionic conductance stable solid electrolyte.
[embodiment]
Embodiment 1
The flask that will have mixer is used nitrogen replacement; Add average grain diameter and be 4 μ m lithium sulfide (Idemitsu Kosen Co., Ltd.) 1.55g, phosphorus pentasulfide (Aldrich company) 3.46g, moisture is made as the xylenes (Wako Pure Chemical Industries, Ltd.) of the 50ml of 10ppm, 140 ℃ of contacts 24 hours.
Solid constituent is utilized isolated by filtration,, produce solid electrolyte 120 ℃ of vacuumizes 40 minutes.The ionic conductance of the solid electrolyte of gained is 2.2 * 10
-6S/cm.In addition; The result of X-ray diffraction
is; Beyond deriving from non-crystal dizzy pattern, do not observe the peak, affirmation is a solid electrolyte glass.
In addition, the particle diameter of lithium sulfide is to use laser diffraction and scattering formula particle size distribution device LMS-30 (SEISHIN enterprise of Co., Ltd.) to measure.
In addition, ionic conductance is measured according to following method.
Solid electrolyte is filled in the tablet forming machine, applies the pressure of 4～6MPa and obtain formed body.Then; Through having mixed two sides that the composite material of carbon and solid electrolyte is placed in formed body at 1: 1 as electrode with weight ratio; Utilize the tablet forming machine to exert pressure once more, and be made into the formed body (the about 10mm of diameter, the about 1mm of thickness) that conductivity is measured usefulness.Utilize AC impedance to measure to this formed body and carry out ionic conductance mensuration.The value of conductivity adopts 25 ℃ numerical value.
Embodiment 2
The solid electrolyte of making among the embodiment 1 further carried out 300 ℃, 5 hours heat treated under nitrogen atmosphere.
The ionic conductance of the solid electrolyte after the heat treated is 2.1 * 10
-4S/cm.
The result that X-ray diffraction is measured is, observes the peak at 2 θ=17.8,18.2,19.8,21.8,23.8,25.9,29.5,30.0deg, though be a spot of, can confirm it is the solid electrolyte glass pottery.
Embodiment 3
Except as lithium sulfide, using the average grain diameter of utilizing jet pulverizer (AISHINNanotechnology company) to pulverize in advance is beyond the lithium sulfide of 0.3 μ m, has made solid electrolyte with embodiment 1 identically.The ionic conductance of this solid electrolyte is 2.0 * 10
-5S/cm.The result of X-ray diffraction
is; Beyond deriving from non-crystal dizzy pattern, do not observe the peak, can confirm it is solid electrolyte glass.
Embodiment 4
With the solid electrolyte of making among the embodiment 3 300 ℃ of heat treated 5 hours.The ionic conductance of the solid electrolyte after the heat treated is 8.2 * 10
-4S/cm.The result that X-ray diffraction is measured is, observes the peak at 2 θ=17.8,18.2,19.8,21.8,23.8,25.9,29.5,30.0deg, can confirm it is the solid electrolyte glass pottery.
Embodiment 5
The average grain diameter that to utilize jet pulverizer (AISHIN Nanotechnology company) to pulverize in advance be lithium sulfide (Idemitsu Kosen Co., Ltd.) 1.55g, phosphorus pentasulfide 3.46g and the moisture of 0.3 μ m be toluene (Wako Pure Chemical Industries, Ltd.) 50ml of 7ppm add with inside with nitrogen replacement the autoclave of band mixer in, under 190 ℃, make it to contact 24 hours.
, solid constituent utilized isolated by filtration,, made solid electrolyte 150 ℃ of following vacuumizes 120 minutes thereafter.
The ionic conductance of this solid electrolyte is 4.0 * 10
-4S/cm.The result of X-ray diffraction
is; Beyond deriving from non-crystal dizzy pattern, do not observe the peak, can confirm it is solid electrolyte glass.
Embodiment 6
With the solid electrolyte of making among the embodiment 5 300 ℃ of heat treated 5 hours.The ionic conductance of the solid electrolyte after the heat treated is 1.1 * 10
-3S/cm.The result that X-ray diffraction is measured is, observes the peak at 2 θ=17.8,18.2,19.8,21.8,23.8,25.9,29.5,30.0deg, can confirm it is the solid electrolyte glass pottery.
Embodiment 7
As used solvent, replace toluene and use the hexane that amount of moisture is reduced to 6ppm, will contact temperature and be made as 78 ℃, will be made as time of contact 48 hours, in addition, make with embodiment 5 identically, made solid electrolyte.The ionic conductance of this solid electrolyte is 6.5 * 10
-5S/cm is 3.3 * 10 at the ionic conductance of 300 ℃ of following heat treated after 5 hours further
-4S/cm.The result that X-ray diffraction is measured is, observes the peak at 2 θ=17.8,18.2,19.8,21.8,23.8,25.9,29.5,30.0deg, can confirm it is the solid electrolyte glass pottery.
Embodiment 8
Be made as 88 ℃ except contacting temperature, will be made as time of contact beyond 40 hours, make identically, made solid electrolyte with embodiment 7.The ionic conductance of this solid electrolyte is 7.7 * 10
-5S/cm is 5.3 * 10 at the ionic conductance of 300 ℃ of following heat treated after 5 hours further
-4S/cm.The result that X-ray diffraction is measured is, observes the peak at 2 θ=17.8,18.2,19.8,21.8,23.8,25.9,29.5,30.0deg, can confirm it is the solid electrolyte glass pottery.
Embodiment 9
Except as used solvent, replace toluene and use the decane that amount of moisture is reduced to 5ppm, will contact temperature and be made as 250 ℃; To be made as time of contact 12 hours; The vacuumize temperature is made as beyond 180 ℃, makes identically, made solid electrolyte with embodiment 5.The ionic conductance of this solid electrolyte is 6.2 * 10
-5S/cm is 9.5 * 10 in the glass ceramics of 300 ℃ of following heat treated after 5 hours further
-4S/cm.
Embodiment 10
Except as lithium sulfide, having used average grain diameter is that the lithium sulfide (three associations change into corporate system) of 12 μ m in addition, has been made solid electrolyte with embodiment 1 identically.The ionic conductance of this solid electrolyte is 1.4 * 10
-6S/cm.The result of X-ray diffraction
is; Beyond deriving from non-crystal dizzy pattern, do not observe the peak, can confirm it is solid electrolyte glass.In addition, the ionic conductance that under nitrogen atmosphere, has carried out the solid electrolyte after 300 ℃, 5 hours the heat treated is 1.2 * 10
-5S/cm.
The result that X-ray diffraction is measured is, can observe the peak at 2 θ=17.8,18.2,19.8,21.8,23.8,25.9,29.5,30.0deg, though be a spot of, can confirm it is the solid electrolyte glass pottery.
Embodiment 11
Except as lithium sulfide, having used average grain diameter is that the lithium sulfide (three associations change into corporate system) of 8 μ m in addition, has been made solid electrolyte with embodiment 1 identically.The ionic conductance of this solid electrolyte is 3.1 * 10
-6S/cm.In addition, the ionic conductance that under nitrogen atmosphere, has carried out the solid electrolyte after 300 ℃, 5 hours the heat treated is 9.5 * 10
-6S/cm.
The result that X-ray diffraction is measured is, can observe the peak at 2 θ=17.8,18.2,19.8,21.8,23.8,25.9,29.5,30.0deg, though be a spot of, can confirm it is the solid electrolyte glass pottery.
Comparative example 1
The interior nitrogen replacement of using of flask that will have mixer; The adding average grain diameter is that lithium sulfide 1.55g, phosphorus pentasulfide 3.46g and the moisture of 4 μ m is N-N-methyl-2-2-pyrrolidone N-(Wako Pure Chemical Industries, Ltd.) 50ml of 5ppm, under 140 ℃, makes it to contact 24 hours.
, solid constituent utilized isolated by filtration, 150 ℃ of following vacuumizes 120 minutes thereafter.The ionic conductance of this solid is 3.7 * 10
-7S/cm.The result of X-ray diffraction
is; Beyond deriving from non-crystal dizzy pattern, do not observe the peak, can confirm it is solid electrolyte glass.
Is 3.4 * 10 with above-mentioned solid electrolyte glass at the ionic conductance of the solid electrolyte of 300 ℃ of following heat treated after 5 hours
-6S/cm.
Utilize possibility in the industry
Utilize manufacturing approach of the present invention, can under lower temperature, not use special installation ground to make lithium-ion-conducting solid electrolyte.
Claims (3)
1. method for producing lithium ion conductive solid electrolyte; It is characterized in that; In the method, comprise make lithium sulfide in the hydrocarbon system solvent be selected from phosphoric sulfide, germanium sulfide, silicon sulfide and sulfuration boron in more than one compound contact 5 minutes at 80 ℃～300 ℃～50 hours operation
With respect to said more than one the total of compound that is selected from phosphoric sulfide, germanium sulfide, silicon sulfide and the sulfuration boron, the addition of said lithium sulfide is 30～95mol%,
With respect to 1 liter of said hydrocarbon system solvent, said more than one the total addition of compound that is selected from phosphoric sulfide, germanium sulfide, silicon sulfide and the sulfuration boron is 0.001～1Kg.
2. method for producing lithium ion conductive solid electrolyte according to claim 1 wherein, carries out heat treated with 200 ℃～400 ℃ temperature with the solid electrolyte that utilizes said contact operation to obtain again.
3. method for producing lithium ion conductive solid electrolyte according to claim 1 and 2, wherein, the average grain diameter of said lithium sulfide is below the 10 μ m.
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|---|---|---|---|
| JP2007-265523 | 2007-10-11 | ||
| JP2007265523 | 2007-10-11 | ||
| PCT/JP2008/067126 WO2009047977A1 (en) | 2007-10-11 | 2008-09-22 | Method for producing lithium ion conductive solid electrolyte |
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|---|---|
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| CN101821894B true CN101821894B (en) | 2012-12-19 |
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| EP (1) | EP2211415B1 (en) |
| JP (2) | JP5270563B2 (en) |
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| TW200923972A (en) | 2009-06-01 |
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